Hydrocarbon conversion using zeolite SSZ-58

ABSTRACT

The present invention relates to new crystalline zeolite SSZ-58 and processes employing SSZ-58 as a catalyst.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to new crystalline zeolite SSZ-58 andprocesses employing SSZ-58 as a catalyst.

2. State of the Art

Because of their unique sieving characteristics, as well as theircatalytic properties, crystalline molecular sieves and zeolites areespecially useful in applications such as hydrocarbon conversion, gasdrying and separation. Although many different crystalline molecularsieves have been disclosed, there is a continuing need for new zeoliteswith desirable properties for gas separation and drying, hydrocarbon andchemical conversions, and other applications. New zeolites may containnovel internal pore architectures, providing enhanced selectivities inthese processes.

Crystalline aluminosilicates are usually prepared from aqueous reactionmixtures containing alkali or alkaline earth metal oxides, silica, andalumina. Crystalline borosilicates are usually prepared under similarreaction conditions except that boron is used in place of aluminum. Byvarying the synthesis conditions and the composition of the reactionmixture, different zeolites can often be formed.

SUMMARY OF THE INVENTION

The present invention is directed to a family of crystalline molecularsieves with unique properties, referred to herein as “zeolite SSZ-58” orsimply “SSZ-58”. Preferably, SSZ-58 is obtained in its silicate,aluminosilicate, titanosilicate, vanadosilicate or borosilicate form.The term “silicate” refers to a zeolite having a high mole ratio ofsilicon oxide relative to aluminum oxide, preferably a mole ratiogreater than 100, including zeolites comprised entirely of siliconoxide. As used herein, the term “aluminosilicate” refers to a zeolitecontaining both alumina and silica and the term “borosilicate” refers toa zeolite containing oxides of both boron and silicon.

The present invention provides a process for converting hydrocarbonscomprising contacting a hydrocarbonaceous feed at hydrocarbon convertingconditions with a catalyst comprising the zeolite of this invention. Thezeolite may be predominantly in the hydrogen form. It may also besubstantially free of acidity.

Further provided by the present invention is a hydrocracking processcomprising contacting a hydrocarbon feedstock under hydrocrackingconditions with a catalyst comprising the zeolite of this invention,preferably predominantly in the hydrogen form.

This invention also includes a dewaxing process comprising contacting ahydrocarbon feedstock under dewaxing conditions with a catalystcomprising the zeolite of this invention, preferably predominantly inthe hydrogen form.

The present invention also includes a process for improving theviscosity index of a dewaxed product of waxy hydrocarbon feedscomprising contacting the waxy hydrocarbon feed under isomerizationdewaxing conditions with a catalyst comprising the zeolite of thisinvention, preferably predominantly in the hydrogen form.

The present invention further includes a process for producing a C₂₀₊lube oil from a C₂₀₊ olefin feed comprising isomerizing said olefin feedunder isomerization conditions over a catalyst comprising at least oneGroup VIII metal and the zeolite of this invention. The zeolite may bepredominantly in the hydrogen form.

In accordance with this invention, there is also provided a process forcatalytically dewaxing a hydrocarbon oil feedstock boiling above about350° F. and containing straight chain and slightly branched chainhydrocarbons comprising contacting said hydrocarbon oil feedstock in thepresence of added hydrogen gas at a hydrogen pressure of about 15-3000psi with a catalyst comprising at least one Group VIII metal and thezeolite of this invention, preferably predominantly in the hydrogenform. The catalyst may be a layered catalyst comprising a first layercomprising at least one Group VIII metal and the zeolite of thisinvention, and a second layer comprising an aluminosilicate zeolitewhich is more shape selective than the zeolite of said first layer.

Also included in the present invention is a process for preparing alubricating oil which comprises hydrocracking in a hydrocracking zone ahydrocarbonaceous feedstock to obtain an effluent comprising ahydrocracked oil, and catalytically dewaxing said effluent comprisinghydrocracked oil at a temperature of at least about 400° F. and at apressure of from about 15 psig to about 3000 psig in the presence ofadded hydrogen gas with a catalyst comprising at least one Group VIIImetal and the zeolite of this invention. The zeolite may bepredominantly in the hydrogen form.

Further included in this invention is a process for isomerizationdewaxing a raffinate comprising contacting said raffinate in thepresence of added hydrogen with a catalyst comprising at least one GroupVIII metal and the zeolite of this invention. The raffinate may bebright stock, and the zeolite may be predominantly in the hydrogen form.

Also included in this invention is a process for increasing the octaneof a hydrocarbon feedstock to produce a product having an increasedaromatics content comprising contacting a hydrocarbonaceous feedstockwhich comprises normal and slightly branched hydrocarbons having aboiling range above about 40° C. and less than about 200° C., underaromatic conversion conditions with a catalyst comprising the zeolite ofthis invention made substantially free of acidity by neutralizing saidzeolite with a basic metal. Also provided in this invention is such aprocess wherein the zeolite contains a Group VIII metal component.

Also provided by the present invention is a catalytic cracking processcomprising contacting a hydrocarbon feedstock in a reaction zone undercatalytic cracking conditions in the absence of added hydrogen with acatalyst comprising the zeolite of this invention, preferablypredominantly in the hydrogen form. Also included in this invention issuch a catalytic cracking process wherein the catalyst additionallycomprises a large pore crystalline cracking component.

This invention further provides an isomerization process for isomerizingC₄ to C₇ hydrocarbons, comprising contacting a feed having normal andslightly branched C₄ to C₇ hydrocarbons under isomerizing conditionswith a catalyst comprising the zeolite of this invention, preferablypredominantly in the hydrogen form. The zeolite may be impregnated withat least one Group VIII metal, preferably platinum. The catalyst may becalcined in a steam/air mixture at an elevated temperature afterimpregnation of the Group VIII metal.

Also provided by the present invention is a process for alkylating anaromatic hydrocarbon which comprises contacting under alkylationconditions at least a molar excess of an aromatic hydrocarbon with a C₂to C₂₀ olefin under at least partial liquid phase conditions and in thepresence of a catalyst comprising the zeolite of this invention,preferably predominantly in the hydrogen form. The olefin may be a C₂ toC₄ olefin, and the aromatic hydrocarbon and olefin may be present in amolar ratio of about 4:1 to about 20:1, respectively. The aromatichydrocarbon may be selected from the group consisting of benzene,toluene, ethylbenzene, xylene, naphthalene, naphthalene derivatives,such as dimethylnaphthalene, or mixtures thereof.

Further provided in accordance with this invention is a process fortransalkylating an aromatic hydrocarbon which comprises contacting undertransalkylating conditions an aromatic hydrocarbon with a polyalkylaromatic hydrocarbon under at least partial liquid phase conditions andin the presence of a catalyst comprising the zeolite of this invention,preferably predominantly in the hydrogen form. The aromatic hydrocarbonand the polyalkyl aromatic hydrocarbon may be present in a molar ratioof from about 1:1 to about 25:1, respectively.

The aromatic hydrocarbon may be selected from the group consisting ofbenzene, toluene, ethylbenzene, xylene, or mixtures thereof, and thepolyalkyl aromatic hydrocarbon may be a dialkylbenzene.

Further provided by this invention is a process to convert paraffins toaromatics which comprises contacting paraffins under conditions whichcause paraffins to convert to aromatics with a catalyst comprising thezeolite of this invention, said catalyst comprising gallium, zinc, or acompound of gallium or zinc.

In accordance with this invention there is also provided a process forisomerizing olefins comprising contacting said olefin under conditionswhich cause isomerization of the olefin with a catalyst comprising thezeolite of this invention.

Further provided in accordance with this invention is a process forisomerizing an isomerization feed comprising an aromatic C₈ stream ofxylene isomers or mixtures of xylene isomers and ethylbenzene, wherein amore nearly equilibrium ratio of ortho-, meta- and para-xylenes isobtained, said process comprising contacting said feed underisomerization conditions with a catalyst comprising the zeolite of thisinvention.

The present invention further provides a process for oligomerizingolefins comprising contacting an olefin feed under oligomerizationconditions with a catalyst comprising the zeolite of this invention.

This invention also provides a process for converting lower alcohols andother oxygenated hydrocarbons comprising contacting said lower alcoholor other oxygenated hydrocarbon with a catalyst comprising the zeoliteof this invention under conditions to produce liquid products.

Further provided in accordance with the present invention is a processfor the production of higher molecular weight hydrocarbons from lowermolecular weight hydrocarbons comprising the steps of:

(a) introducing into a reaction zone a lower molecular weighthydrocarbon-containing gas and contacting said gas in said zone underC₂₊ hydrocarbon synthesis conditions with the catalyst and a metal ormetal compound capable of converting the lower molecular weighthydrocarbon to a higher molecular weight hydrocarbon; and

(b) withdrawing from said reaction zone a higher molecular weighthydrocarbon-containing stream.

DETAILED DESCRIPTION OF THE INVENTION

The present invention comprises a family of crystalline, zeolitesdesignated herein “zeolite SSZ-58” or simply “SSZ-58”. SSZ-58 isbelieved to be a large pore zeolite. As used herein, the term “largepore” means having an average pore size diameter greater than about 6.5Angstroms, preferably from about 7 Angstroms to about 8 Angstroms.

In preparing SSZ-58 zeolites, a N-butyl-N-cyclooctylpyrrolidinium cationor N-propyl-cyclooctylpyrrolidinium cation is used as a crystallizationtemplate. In general, SSZ-58 is prepared by contacting an active sourceof one or more oxides selected from the group consisting of monovalentelement oxides, divalent element oxides, trivalent element oxides, andtetravalent element oxides with the templating agent.

SSZ-58 is prepared from a reaction mixture having the composition shownin Table A below.

TABLE A Reaction Mixture Typical Preferred YO₂/W_(a)O_(b) >20 35-65OH—/YO₂ 0.10-0.50 0.15-0.25 Q/YO₂ 0.05-0.50 0.10-0.20 M_(2/n)/YO₂0.02-0.40 0.10-0.30 H₂O/YO₂  25-100 30-50

wherein Y is silicon, germanium or a mixture thereof; W is aluminum,gallium, iron, boron, titanium, indium, vanadium or mixtures thereof;and a is 1 or 2, and b is 2 when a is 1 (i.e., W is tetravalent) and bis 3 when a is 2 (i.e., W is trivalent).

In practice, SSZ-58 is prepared by a process comprising:

(a) preparing an aqueous solution containing sources of at least oneoxide capable of forming a crystalline molecular sieve and aN-butyl-N-cyclooctylpyrrolidinium cation orN-propyl-cyclooctylpyrrolidinium cation having an anionic counterionwhich is not detrimental to the formation of SSZ-58;

(b) maintaining the aqueous solution under conditions sufficient to formcrystals of SSZ-58; and

(c) recovering the crystals of SSZ-58.

Accordingly, SSZ-58 may comprise the crystalline material and thetemplating agent in combination with metallic and non-metallic oxidesbonded in tetrahedral coordination through shared oxygen atoms to form across-linked three dimensional crystal structure. The metallic andnon-metallic oxides comprise one or a combination of oxides of a firsttetravalent element(s), and one or a combination of a second tetravalentelement(s) different from the first tetravalent element(s), trivalentelement(s), pentavalent element(s) or mixture thereof. The firsttetravalent element(s) is preferably selected from the group consistingof silicon, germanium and combinations thereof. More preferably, thefirst tetravalent element is silicon. The second tetravalent element(which is different from the first tetravalent element), trivalentelement and pentavalent element is preferably selected from the groupconsisting of aluminum, gallium, iron, boron, titanium, indium, vanadiumand combinations thereof. More preferably, the second trivalent ortetravalent element is aluminum or boron.

Typical sources of aluminum oxide for the reaction mixture includealuminates, alumina, aluminum colloids, aluminum oxide coated on silicasol, hydrated alumina gels such as Al(OH)₃ and aluminum compounds suchas AlCl₃ and Al₂(SO₄)₃. Typical sources of silicon oxide includesilicates, silica hydrogel, silicic acid, fumed silica, colloidalsilica, tetra-alkyl orthosilicates, and silica hydroxides. Boron, aswell as gallium, germanium, titanium, indium, vanadium and iron, can beadded in forms corresponding to their aluminum and silicon counterparts.

A source zeolite reagent may provide a source of aluminum or boron. Inmost cases, the source zeolite also provides a source of silica. Thesource zeolite in its dealuminated or deboronated form may also be usedas a source of silica, with additional silicon added using, for example,the conventional sources listed above. Use of a source zeolite reagentas a source of alumina for the present process is more completelydescribed in U.S. Pat. No. 5,225,179, issued Jul. 6, 1993 to Nakagawaentitled “Method of Making Molecular Sieves”, the disclosure of which isincorporated herein by reference.

Typically, an alkali metal hydroxide and/or an alkaline earth metalhydroxide, such as the hydroxide of sodium, potassium, lithium, cesium,rubidium, calcium, and magnesium, is used in the reaction mixture;however, this component can be omitted so long as the equivalentbasicity is maintained. The templating agent may be used to providehydroxide ion. Thus, it may be beneficial to ion exchange, for example,the halide for hydroxide ion, thereby reducing or eliminating the alkalimetal hydroxide quantity required. The alkali metal cation or alkalineearth cation may be part of the as-synthesized crystalline oxidematerial, in order to balance valence electron charges therein.

The reaction mixture is maintained at an elevated temperature until thecrystals of the SSZ-58 zeolite are formed. The hydrothermalcrystallization is usually conducted under autogenous pressure, at atemperature between 100° C. and 200° C., preferably between 135° C. and160° C. The crystallization period is typically greater than 1-day andpreferably from about 3 days to about 20 days.

Preferably, the zeolite is prepared using mild stirring or agitation.

During the hydrothermal crystallization step, the SSZ-58 crystals can beallowed to nucleate spontaneously from the reaction mixture. The use ofSSZ-58 crystals as seed material can be advantageous in decreasing thetime necessary for complete crystallization to occur. In addition,seeding can lead to an increased purity of the product obtained bypromoting the nucleation and/or formation of SSZ-58 over any undesiredphases. When used as seeds, SSZ-58 crystals are added in an amountbetween 0.1 and 10% of the weight of silica used in the reactionmixture.

Once the zeolite crystals have formed, the solid product is separatedfrom the reaction mixture by standard mechanical separation techniquessuch as filtration. The crystals are water-washed and then dried, e.g.,at 90° C. to 150° C. for from 8 to 24 hours, to obtain theas-synthesized SSZ-58 zeolite crystals. The drying step can be performedat atmospheric pressure or under vacuum.

SSZ-58 as prepared has a mole ratio of an oxide selected from siliconoxide, germanium oxide and mixtures thereof to an oxide selected fromaluminum oxide, gallium oxide, iron oxide, boron oxide, titanium oxide,indium oxide, vanadium oxide and mixtures thereof greater than about 20;and has, after calcination, the X-ray diffraction lines of Table IIbelow. SSZ-58 further has a composition, as synthesized (i.e., prior toremoval of the templating agent from the zeolite) and in the anhydrousstate, in terms of mole ratios, shown in Table B below.

TABLE B As-Synthesized SSZ-58 YO₂/W_(c)O_(d) >20 M_(2/n)/YO₂ 0.01-0.03H₂O/YO₂ 0.02-0.05

where Y, W, M, n and Q are as defined above and c is 1 or 2; d is 2 whenc is 1 (i.e., W is tetravalent) or d is 3 or 5 when c is 2 (i.e., d is 3when W is trivalent or 5 when W is pentavalent).

SSZ-58 can be made essentially aluminum free, i.e., having a silica toalumina mole ratio of ∞. A method of increasing the mole ratio of silicato alumina is by using standard acid leaching or chelating treatments.However, essentially aluminum-free SSZ-58 can be synthesized directlyusing essentially aluminum-free silicon sources as the main tetrahedralmetal oxide component, if boron is also present. SSZ-58 can also beprepared directly as either an aluminosilicate or a borosilicate.

Lower silica to alumina ratios may also be obtained by using methodswhich insert aluminum into the crystalline framework. For example,aluminum insertion may occur by thermal treatment of the zeolite incombination with an alumina binder or dissolved source of alumina. Suchprocedures are described in U.S. Pat. No. 4,559,315, issued on Dec. 17,1985 to Chang et al.

It is believed that SSZ-58 is comprised of a new framework structure ortopology which is characterized by its X-ray diffraction pattern. SSZ-58zeolites, as-synthesized, have a crystalline structure whose X-raypowder diffraction pattern exhibit the characteristic lines shown inTable I and is thereby distinguished from other zeolites.

TABLE I As-Synthesized SSZ-58 2 Theta (deg.)^((a)) d RelativeIntensity^((b)) 7.1 12.4 S 7.7 11.5 M 9.9 8.93 M 10.5 8.42 W 12.1 7.31 M17.3 5.12 W 19.7 4.50 M 21.0 4.23 S 21.9 4.06 M 22.35 3.97 VS^((a))±0.15 ^((b))The X-ray patterns provided are based on a relativeintensity scale in which the strongest line in the X-ray pattern isassigned a value of 100: W (weak) is less than 20; M (medium) is between20 and 40; S (strong) is between 40 and 60; VS (very strong) is greaterthan 60.

Table IA below shows the X-ray powder diffraction lines foras-synthesized SSZ-58 including actual relative intensities.

TABLE IA As-Synthesized SSZ-58 2 Theta (deg.)^((a)) d I/I₀ x 100 6.9012.80 6 (Sh) 7.06 12.51 39 7.72 1.44 16 9.86 8.963 10 (Sh) 9.96 8.874 1310.46 8.450 10 12.10 7.309 18 14.06 6.294 9 14.21 6.228 7 (Sh) 15.465.727 5 15.68 5.647 6 16.12 5.494 4 17.24 5.139 14 17.36 5.104 7 (Sh)18.76 4.726 15 18.92 4.687 16 19.72 4.498 30 20.22 4.388 14 20.70 4.28816 21.00 4.227 63 21.16 4.195 14 21.26 4.176 12 (Sh) 21.88 4.059 2622.28 3.987 61 (Sh) 22.24 3.962 100 22.66 3.921 26 23.02 3.860 9 23.283.818 5 23.50 3.783 17 23.68 3.754 13 24.34 3.654 5 25.12 3.542 11 25.543.485 7 25.72 3.461 4 (Sh) 26.12 3.409 8 26.58 3.351 7 27.30 3.264 1127.58 3.232 7 27.94 3.191 5 28.50 3.129 8 (Sh) 28.62 3.117 11 29.183.058 2 29.86 2.990 5 30.08 2.968 5 30.88 2.894 3 31.46 2.842 2 31.742.817 4 32.48 2.755 1 32.59 2.746 2 32.76 2.732 3 33.14 2.701 4 33.562.668 3 33.80 2.650 2 34.82 2.574 2 35.12 2.553 1 35.38 2.535 3 35.822.505 6 36.50 2.460 6 37.74 2.382 4 37.94 2.370 2 (Sh) 38.44 2.340 239.29 2.291 2 39.62 2.273 1 41.10 2.194 1 43.12 2.096 2 43.30 2.086 543.50 2.079 2 ^((a))±0.15

After calcination, the SSZ-58 zeolites have a crystalline structurewhose X-ray powder diffraction pattern include the characteristic linesshown in Table II:

TABLE II Calcined SSZ-58 2 Theta (deg.)^((a)) d Relative Intensity 7.112.4 VS 7.7 11.5 M 9.9 8.93 M 10.5 8.42 M 12.1 7.31 W 17.3 5.12 W 19.84.48 M 21.0 4.23 S 21.9 4.06 M 22.4 3.97 S ^((a))±0.15

Table IIA below shows the X-ray powder diffraction lines for calcinedSSZ-58 including actual relative intensities.

TABLE IIA Calcined SSZ-58 Two Theta (deg.)^((a)) d I/Io x 100 6.88 12.8417 (Sh) 7.06 12.51 100 7.70 11.47 22 9.86 8.963 20 (Sh) 9.98 8.856 3510.48 8.435 15 12.12 7.297 9 14.20 6.232 11 15.48 5.720 6 15.70 5.640 1015.84 5.590 7 16.14 5.487 6 17.24 5.139 11 17.37 5.101 4 18.78 4.721 718.96 4.677 14 19.76 4.489 23 20.26 4.380 8 20.70 4.287 13 21.02 4.22340 21.22 4.184 9 (Sh) 21.90 4.055 18 22.35 3.975 39 (Sh) 22.46 3.955 6422.70 3.914 18 23.04 3.857 3 23.28 3.818 3 23.54 3.776 13 23.74 3.745 824.38 3.648 3 25.16 3.537 8 25.60 3.477 5 25.78 3.453 4 (Sh) 26.14 3.4065 26.64 3.343 6 27.34 3.259 6 27.64 3.225 6 27.98 3.186 4 28.58 3.121 7(Sh) 28.68 3.110 8 29.20 3.056 1 29.88 2.988 4 30.19 2.958 3 30.92 2.8902 31.48 2.840 2 31.74 2.817 3 32.54 2.750 1 32.76 2.731 1 33.18 2.698 233.62 2.664 2 33.86 2.645 2 34.88 2.570 1 35.20 2.548 1 35.42 2.532 235.90 2.499 5 36.54 2.457 4 37.80 2.378 3 38.00 2.366 2 (Sh) 38.50 2.3361 39.30 2.291 1 43.20 2.092 2 43.42 2.082 4 43.53 2.077 3

The X-ray powder diffraction patterns were determined by standardtechniques. The radiation was the K-alpha/doublet of copper. The peakheights and the positions, as a function of 2θ where θ is the Braggangle, were read from the relative intensities of the peaks, and d, theinterplanar spacing in Angstroms corresponding to the recorded lines,can be calculated.

The variation in the scattering angle (two theta) measurements, due toinstrument error and to differences between individual samples, isestimated at ±0.20 degrees.

The X-ray diffraction pattern of Table I is representative of“as-synthesized” or “as-made” SSZ-58 zeolites. Minor variations in thediffraction pattern can result from variations in the silica-to-aluminaor silica-to-boron mole ratio of the particular sample due to changes inlattice constants. In addition, sufficiently small crystals will affectthe shape and intensity of peaks, leading to significant peakbroadening.

Representative peaks from the X-ray diffraction pattern of calcinedSSZ-58 are shown in Table II. Calcination can also result in changes inthe intensities of the peaks as compared to patterns of the “as-made”material, as well as minor shifts in the diffraction pattern. Thezeolite produced by exchanging the metal or other cations present in thezeolite with various other cations (such as H⁺ or NH₄ ⁺) yieldsessentially the same diffraction pattern, although again, there may beminor shifts in the interplanar spacing and variations in the relativeintensities of the peaks. Notwithstanding these minor perturbations, thebasic crystal lattice remains unchanged by these treatments.

Crystalline SSZ-58 can be used as-synthesized, but preferably will bethermally treated (calcined). Usually, it is desirable to remove thealkali metal cation by ion exchange and replace it with hydrogen,ammonium, or any desired metal ion. The zeolite can be leached withchelating agents, e.g., EDTA or dilute acid solutions, to increase thesilica to alumina mole ratio. The zeolite can also be steamed; steaminghelps stabilize the crystalline lattice to attack from acids.

The zeolite can be used in intimate combination with hydrogenatingcomponents, such as tungsten, vanadium molybdenum, rhenium, nickelcobalt, chromium, manganese, or a noble metal, such as palladium orplatinum, for those applications in which ahydrogenation-dehydrogenation function is desired.

Metals may also be introduced into the zeolite by replacing some of thecations in the zeolite with metal cations via standard ion exchangetechniques (see, for example, U.S. Pat. No. 3,140,249 issued Jul. 7,1964 to Plank et al.; U.S. Pat. No. 3,140,251 issued Jul. 7, 1964 toPlank et al.; and U.S. Pat. No. 3,140,253 issued Jul. 7, 1964 to Planket al.). Typical replacing cations can include metal cations, e.g., rareearth, Group IA, Group IIA and Group VIII metals, as well as theirmixtures. Of the replacing metallic cations, cations of metals such asrare earth, Mn, Ca, Mg, Zn, Cd, Pt, Pd, Ni, Co, Ti, Al, Sn, and Fe areparticularly preferred.

The hydrogen, ammonium, and metal components can be ion-exchanged intothe SSZ-58. The zeolite can also be impregnated with the metals, or, themetals can be physically and intimately admixed with the zeolite usingstandard methods known to the art.

Typical ion-exchange techniques involve contacting the synthetic zeolitewith a solution containing a salt of the desired replacing cation orcations. Although a wide variety of salts can be employed, chlorides andother halides, acetates, nitrates, and sulfates are particularlypreferred. The zeolite is usually calcined prior to the ion-exchangeprocedure to remove the organic matter present in the channels and onthe surface, since this results in a more effective ion exchange.Representative ion exchange techniques are disclosed in a wide varietyof patents including U.S. Pat. No. 3,140,249 issued on Jul. 7, 1964 toPlank et al.; U.S. Pat. No. 3,140,251 issued on Jul. 7, 1964 to Plank etal.; and U.S. Pat. No. 3,140,253 issued on Jul. 7, 1964 to Plank et al.

Following contact with the salt solution of the desired replacingcation, the zeolite is typically washed with water and dried attemperatures ranging from 65° C. to about 200° C. After washing, thezeolite can be calcined in air or inert gas at temperatures ranging fromabout 200° C. to about 800° C. for periods of time ranging from 1 to 48hours, or more, to produce a catalytically active product especiallyuseful in hydrocarbon conversion processes.

Regardless of the cations present in the synthesized form of SSZ-58, thespatial arrangement of the atoms which form the basic crystal lattice ofthe zeolite remains essentially unchanged.

SSZ-58 can be formed into a wide variety of physical shapes. Generallyspeaking, the zeolite can be in the form of a powder, a granule, or amolded product, such as extrudate having a particle size sufficient topass through a 2-mesh (Tyler) screen and be retained on a 400-mesh(Tyler) screen. In cases where the catalyst is molded, such as byextrusion with an organic binder, the aluminosilicate can be extrudedbefore drying, or, dried or partially dried and then extruded.

SSZ-58 can be composited with other materials resistant to thetemperatures and other conditions employed in organic conversionprocesses. Such matrix materials include active and inactive materialsand synthetic or naturally occurring zeolites as well as inorganicmaterials such as clays, silica and metal oxides. Examples of suchmaterials and the manner in which they can be used are disclosed in U.S.Pat. No. 4,910,006, issued May 20, 1990 to Zones et al., and U.S. Pat.No. 5,316,753, issued May 31, 1994 to Nakagawa, both of which areincorporated by reference herein in their entirety.

Hydrocarbon Conversion Processes

SSZ-58 zeolites are useful in hydrocarbon conversion reactions.Hydrocarbon conversion reactions are chemical and catalytic processes inwhich carbon containing compounds are changed to different carboncontaining compounds. Examples of hydrocarbon conversion reactions inwhich SSZ-58 are expected to be useful include hydrocracking, dewaxing,catalytic cracking and olefin and aromatics formation reactions. Thecatalysts are also expected to be useful in other petroleum refining andhydrocarbon conversion reactions such as isomerizing n-paraffins andnaphthenes, polymerizing and oligomerizing olefinic or acetyleniccompounds such as isobutylene and butene-1, reforming, isomerizingpolyalkyl substituted aromatics (e.g., m-xylene), and disproportionatingaromatics (e.g., toluene) to provide mixtures of benzene, xylenes andhigher methylbenzenes and oxidation reactions. Also included arerearrangement reactions to make various naphthalene derivatives, andforming higher molecular weight hydrocarbons from lower molecular weighthydrocarbons (e.g., methane upgrading). The SSZ-58 catalysts may havehigh selectivity, and under hydrocarbon conversion conditions canprovide a high percentage of desired products relative to totalproducts.

SSZ-58 zeolites can be used in processing hydrocarbonaceous feedstocks.Hydrocarbonaceous feedstocks contain carbon compounds and can be frommany different sources, such as virgin petroleum fractions, recyclepetroleum fractions, shale oil, liquefied coal, tar sand oil, syntheticparaffins from NAO, recycled plastic feedstocks and, in general, can beany carbon containing feedstock susceptible to zeolitic catalyticreactions. Depending on the type of processing the hydrocarbonaceousfeed is to undergo, the feed can contain metal or be free of metals, itcan also have high or low nitrogen or sulfur impurities. It can beappreciated, however, that in general processing will be more efficient(and the catalyst more active) the lower the metal, nitrogen, and sulfurcontent of the feedstock.

The conversion of hydrocarbonaceous feeds can take place in anyconvenient mode, for example, in fluidized bed, moving bed, or fixed bedreactors depending on the types of process desired. The formulation ofthe catalyst particles will vary depending on the conversion process andmethod of operation.

Other reactions which can be performed using the catalyst of thisinvention containing a metal, e.g., a Group VIII metal such platinum,include hydrogenation-dehydrogenation reactions, denitrogenation anddesulfurization reactions.

The following table indicates typical reaction conditions which may beemployed when using catalysts comprising SSZ-58 in the hydrocarbonconversion reactions of this invention. Preferred conditions areindicated in parentheses.

Process Temp., ° C. Pressure LHSV Hydrocracking 175-485 0.5-350 bar 0.1-30 Dewaxing 200-475 15-3000 psig  0.1-20 (250-450) (200-3000)(0.2-10) Aromatics formation 400-600 atm. - 10 bar  0.1-15 (480-550)Cat. cracking 127-885 subatm. -¹  0.5-50 (atm. - 5 atm.) Oligomerization232-649² 0.1-50 atm.^(2,3)  0.2-50²  10-232⁴ — 0.05-20⁵  (27-204)⁴ —(0.1-10)⁵ Paraffins to aromatics 100-700 0-1000 psig  0.5-40⁵Condensation of alcohols 260-538 0.5-1000 psig  0.5-50⁵ Isomerization 93-538 50-1000 psig   1-10 (204-315)   (1-4) Xylene isomerization260-593² 0.5-50 atm.²  0.1-100⁵ (315-566)² (1-5 atm)² (0.5-50)⁵  38-371⁴1-200 atm.⁴  0.5-50 ¹Several hundred atmospheres ²Gas phase reaction³Hydrocarbon partial pressure ⁴Liquid phase reaction ⁵WHSV

Other reaction conditions and parameters are provided below.

Hydrocracking

Using a catalyst which comprises SSZ-58, preferably predominantly in thehydrogen form, and a hydrogenation promoter, heavy petroleum residualfeedstocks, cyclic stocks and other hydrocrackate charge stocks can behydrocracked using the process conditions and catalyst componentsdisclosed in the aforementioned U.S. Pat. No. 4,910,006 and U.S. Pat.No. 5,316,753.

The hydrocracking catalysts contain an effective amount of at least onehydrogenation component of the type commonly employed in hydrocrackingcatalysts. The hydrogenation component is generally selected from thegroup of hydrogenation catalysts consisting of one or more metals ofGroup VIB and Group VIII, including the salts, complexes and solutionscontaining such. The hydrogenation catalyst is preferably selected fromthe group of metals, salts and complexes thereof of the group consistingof at least one of platinum, palladium, rhodium, iridium, ruthenium andmixtures thereof or the group consisting of at least one of nickel,molybdenum, cobalt, tungsten, titanium, chromium and mixtures thereof.Reference to the catalytically active metal or metals is intended toencompass such metal or metals in the elemental state or in some formsuch as an oxide, sulfide, halide, carboxylate and the like. Thehydrogenation catalyst is present in an effective amount to provide thehydrogenation function of the hydrocracking catalyst, and preferably inthe range of from 0.05 to 25% by weight.

Dewaxing

SSZ-58, preferably predominantly in the hydrogen form, can be used todewax hydrocarbonaceous feeds by selectively removing straight chainparaffins. Typically, the viscosity index of the dewaxed product isimproved (compared to the waxy feed) when the waxy feed is contactedwith SSZ-58 under isomerization dewaxing conditions.

The catalytic dewaxing conditions are dependent in large measure on thefeed used and upon the desired pour point. Hydrogen is preferablypresent in the reaction zone during the catalytic dewaxing process. Thehydrogen to feed ratio is typically between about 500 and about 30,000SCF/bbl (standard cubic feet per barrel), preferably about 1000 to about20,000 SCF/bbl. Generally, hydrogen will be separated from the productand recycled to the reaction zone. Typical feedstocks include light gasoil, heavy gas oils and reduced crudes boiling above about 350° F.

A typical dewaxing process is the catalytic dewaxing of a hydrocarbonoil feedstock boiling above about 350° F. and containing straight chainand slightly branched chain hydrocarbons by contacting the hydrocarbonoil feedstock in the presence of added hydrogen gas at a hydrogenpressure of about 15-3000 psi with a catalyst comprising SSZ-58 and atleast one Group VIII metal.

The SSZ-58 hydrodewaxing catalyst may optionally contain a hydrogenationcomponent of the type commonly employed in dewaxing catalysts. See theaforementioned U.S. Pat. No. 4,910,006 and U.S. Pat. No. 5,316,753 forexamples of these hydrogenation components.

The hydrogenation component is present in an effective amount to providean effective hydrodewaxing and hydroisomerization catalyst preferably inthe range of from about 0.05 to 5% by weight. The catalyst may be run insuch a mode to increase isodewaxing at the expense of crackingreactions.

The feed may be hydrocracked, followed by dewaxing. This type of twostage process and typical hydrocracking conditions are described in U.S.Pat. No. 4,921,594, issued May 1, 1990 to Miller, which is incorporatedherein by reference in its entirety.

SSZ-58 may also be utilized as a dewaxing catalyst in the form of alayered catalyst. That is, the catalyst comprises a first layercomprising zeolite SSZ-58 and at least one Group VIII metal, and asecond layer comprising an aluminosilicate zeolite which is more shapeselective than zeolite SSZ-58. The use of layered catalysts is disclosedin U.S. Pat. No. 5,149,421, issued Sep. 22, 1992 to Miller, which isincorporated by reference herein in its entirety. The layering may alsoinclude a bed of SSZ-58 layered with a non-zeolitic component designedfor either hydrocracking or hydrofinishing.

SSZ-58 may also be used to dewax raffinates, including bright stock,under conditions such as those disclosed in U.S. Pat. No. 4,181,598,issued Jan. 1, 1980 to Gillespie et al., which is incorporated byreference herein in its entirety.

It is often desirable to use mild hydrogenation (sometimes referred toas hydrofinishing) to produce more stable dewaxed products. Thehydrofinishing step can be performed either before or after the dewaxingstep, and preferably after. Hydrofinishing is typically conducted attemperatures ranging from about 190° C. to about 340° C. at pressuresfrom about 400 psig to about 3000 psig at space velocities (LHSV)between about 0.1 and 20 and a hydrogen recycle rate of about 400 to1500 SCF/bbl. The hydrogenation catalyst employed must be active enoughnot only to hydrogenate the olefins, diolefins and color bodies whichmay be present, but also to reduce the aromatic content. Suitablehydrogenation catalyst are disclosed in U.S. Pat. No. 4,921,594, issuedMay 1, 1990 to Miller, which is incorporated by reference herein in itsentirety. The hydrofinishing step is beneficial in preparing anacceptably stable product (e.g., a lubricating oil) since dewaxedproducts prepared from hydrocracked stocks tend to be unstable to airand light and tend to form sludges spontaneously and quickly.

Lube oil may be prepared using SSZ-58. For example, a C₂₀₊ lube oil maybe made by isomerizing a C₂₊ olefin feed over a catalyst comprisingSSZ-58 in the hydrogen form and at least one Group VIII metal.Alternatively, the lubricating oil may be made by hydrocracking in ahydrocracking zone a hydrocarbonaceous feedstock to obtain an effluentcomprising a hydrocracked oil, and catalytically dewaxing the effluentat a temperature of at least about 400° F. and at a pressure of fromabout 15 psig to about 3000 psig in the presence of added hydrogen gaswith a catalyst comprising SSZ-58 in the hydrogen form and at least oneGroup VIII metal.

Aromatics Formation

SSZ-58 can be used to convert light straight run naphthas and similarmixtures to highly aromatic mixtures. Thus, normal and slightly branchedchained hydrocarbons, preferably having a boiling range above about 40°C. and less than about 200° C., can be converted to products having asubstantial higher octane aromatics content by contacting thehydrocarbon feed with a catalyst comprising SSZ-58. It is also possibleto convert heavier feeds into BTX or naphthalene derivatives of valueusing a catalyst comprising SSZ-58.

The conversion catalyst preferably contains a Group VIII metal compoundto have sufficient activity for commercial use. By Group VIII metalcompound as used herein is meant the metal itself or a compound thereof.The Group VIII noble metals and their compounds, platinum, palladium,and iridium, or combinations thereof can be used. Rhenium or tin or amixture thereof may also be used in conjunction with the Group VIIImetal compound and preferably a noble metal compound. The most preferredmetal is platinum. The amount of Group VIII metal present in theconversion catalyst should be within the normal range of use inreforming catalysts, from about 0.05 to 2.0 weight percent, preferably0.2 to 0.8 weight percent.

It is critical to the selective production of aromatics in usefulquantities that the conversion catalyst be substantially free ofacidity, for example, by neutralizing the zeolite with a basic metal,e.g., alkali metal, compound. Methods for rendering the catalyst free ofacidity are known in the art. See the aforementioned U.S. Pat. No.4,910,006 and U.S. Pat. No. 5,316,753 for a description of such methods.

The preferred alkali metals are sodium, potassium, rubidium and cesium.The zeolite itself can be substantially free of acidity only at veryhigh silica:alumina mole ratios.

Catalytic Cracking

Hydrocarbon cracking stocks can be catalytically cracked in the absenceof hydrogen using SSZ-58, preferably predominantly in the hydrogen form.

When SSZ-58 is used as a catalytic cracking catalyst in the absence ofhydrogen, the catalyst may be employed in conjunction with traditionalcracking catalysts, e.g., any aluminosilicate heretofore employed as acomponent in cracking catalysts. Typically, these are large pore,crystalline aluminosilicates. Examples of these traditional crackingcatalysts are disclosed in the aforementioned U.S. Pat. No. 4,910,006and U.S. Pat. No 5,316,753. When a traditional cracking catalyst (TC)component is employed, the relative weight ratio of the TC to the SSZ-58is generally between about 1:10 and about 500:1, desirably between about1:10 and about 200:1, preferably between about 1:2 and about 50:1, andmost preferably is between about 1:1 and about 20:1. The novel zeoliteand/or the traditional cracking component may be further ion exchangedwith rare earth ions to modify selectivity.

The cracking catalysts are typically employed with an inorganic oxidematrix component. See the aforementioned U.S. Pat. No. 4,910,006 andU.S. Pat. No. 5,316,753 for examples of such matrix components.

Isomerization

The present catalyst is highly active and highly selective forisomerizing C₄ to C₇ hydrocarbons. The activity means that the catalystcan operate at relatively low temperature which thermodynamically favorshighly branched paraffins. Consequently, the catalyst can produce a highoctane product. The high selectivity means that a relatively high liquidyield can be achieved when the catalyst is run at a high octane.

The present process comprises contacting the isomerization catalyst,i.e., a catalyst comprising SSZ-58 in the hydrogen form, with ahydrocarbon feed under isomerization conditions. The feed is preferablya light straight run fraction, boiling within the range of 30° F. to250° F. and preferably from 60° F. to 200° F. Preferably, thehydrocarbon feed for the process comprises a substantial amount of C₄ toC₇ normal and slightly branched low octane hydrocarbons, more preferablyC₅ and C₆ hydrocarbons.

It is preferable to carry out the isomerization reaction in the presenceof hydrogen. Preferably, hydrogen is added to give a hydrogen tohydrocarbon ratio (H₂/HC) of between 0.5 and 10 H₂/HC, more preferablybetween 1 and 8 H₂/HC. See the aforementioned U.S. Pat. No. 4,910,006and U.S. Pat. No. 5,316,753 for a further discussion of isomerizationprocess conditions.

A low sulfur feed is especially preferred in the present process. Thefeed preferably contains less than 10 ppm, more preferably less than 1ppm, and most preferably less than 0.1 ppm sulfur. In the case of a feedwhich is not already low in sulfur, acceptable levels can be reached byhydrogenating the feed in a presaturation zone with a hydrogenatingcatalyst which is resistant to sulfur poisoning. See the aforementionedU.S. Pat. No. 4,910,006 and U.S. Pat. No. 5,316,753 for a furtherdiscussion of this hydrodesulfurization process.

It is preferable to limit the nitrogen level and the water content ofthe feed. Catalysts and processes which are suitable for these purposesare known to those skilled in the art.

After a period of operation, the catalyst can become deactivated bysulfur or coke. See the aforementioned U.S. Pat. No. 4,910,006 and U.S.Pat. No. 5,316,753 for a further discussion of methods of removing thissulfur and coke, and of regenerating the catalyst.

The conversion catalyst preferably contains a Group VIII metal compoundto have sufficient activity for commercial use. By Group VIII metalcompound as used herein is meant the metal itself or a compound thereof.The Group VIII noble metals and their compounds, platinum, palladium,and iridium, or combinations thereof can be used. Rhenium and tin mayalso be used in conjunction with the noble metal. The most preferredmetal is platinum. The amount of Group VIII metal present in theconversion catalyst should be within the normal range of use inisomerizing catalysts, from about 0.05 to 2.0 weight percent, preferably0.2 to 0.8 weight percent.

Alkylation and Transalkylation

SSZ-58 can be used in a process for the alkylation or transalkylation ofan aromatic hydrocarbon. The process comprises contacting the aromatichydrocarbon with a C₂ to C₁₆ olefin alkylating agent or a polyalkylaromatic hydrocarbon transalkylating agent, under at least partialliquid phase conditions, and in the presence of a catalyst comprisingSSZ-58.

SSZ-58 can also be used for removing benzene from gasoline by alkylatingthe benzene as described above and removing the alkylated product fromthe gasoline.

For high catalytic activity, the SSZ-58 zeolite should be predominantlyin its hydrogen ion form. It is preferred that, after calcination, atleast 80% of the cation sites are occupied by hydrogen ions and/or rareearth ions.

Examples of suitable aromatic hydrocarbon feedstocks which may bealkylated or transalkylated by the process of the invention includearomatic compounds such as benzene, toluene and xylene. The preferredaromatic hydrocarbon is benzene. There may be occasions wherenaphthalene or naphthalene derivatives, such as dimethylnaphthalene, maybe desirable. Mixtures of aromatic hydrocarbons may also be employed.

Suitable olefins for the alkylation of the aromatic hydrocarbon arethose containing 2 to 20, preferably 2 to 4, carbon atoms, such asethylene, propylene, butene-1, trans-buten-2 and cis-butene-2, ormixtures thereof. There may be instances where pentenes are desirable.The preferred olefins are ethylene and propylene. Longer chain alphaolefins may be used as well.

When transalkylation is desired, the transalkylating agent is apolyalkyl aromatic hydrocarbon containing two or more alkyl groups thateach may have from 2 to about 4 carbon atoms. For example, suitablepolyalkyl aromatic hydrocarbons include di-, tri-and tetra-alkylaromatic hydrocarbons, such as diethylbenzene, triethylbenzene,diethylmethylbenzene (diethyltoluene), di-isopropylbenzene,di-isopropyltoluene, dibutylbenzene, and the like. Preferred polyalkylaromatic hydrocarbons are the dialkyl benzenes. A particularly preferredpolyalkyl aromatic hydrocarbon is di-isopropylbenzene.

When alkylation is the process conducted, reaction conditions are asfollows. The aromatic hydrocarbon feed should be present instoichiometric excess. It is preferred that molar ratio of aromatics toolefins be greater than four-to-one to prevent rapid catalyst fouling.The reaction temperature may range from 100° F. to 600° F., preferably250° F. to 450° F. The reaction pressure should be sufficient tomaintain at least a partial liquid phase in order to retard catalystfouling. This is typically 50 psig to 1000 psig depending on thefeedstock and reaction temperature. Contact time may range from 10seconds to 10 hours, but is usually from 5 minutes to an hour. Theweight hourly space velocity (WHSV), in terms of grams (pounds) ofaromatic hydrocarbon and olefin per gram (pound) of catalyst per hour,is generally within the range of about 0.5 to 50.

When transalkylation is the process conducted, the molar ratio ofaromatic hydrocarbon will generally range from about 1:1 to 25:1, andpreferably from about 2:1 to 20:1. The reaction temperature may rangefrom about 100° F. to 600° F., but it is preferably about 250° F. to450° F. The reaction pressure should be sufficient to maintain at leasta partial liquid phase, typically in the range of about 50 psig to 1000psig, preferably 300 psig to 600 psig. The weight hourly space velocitywill range from about 0.1 to 10. U.S. Pat. No. 5,082,990 issued on Jan.21, 1992 to Hsieh, et al. describes such processes and is incorporatedherein by reference.

Conversion of Paraffins to Aromatics

SSZ-58 can be used to convert light gas C₂-C₆ paraffins to highermolecular weight hydrocarbons including aromatic compounds. Preferably,the zeolite will contain a catalyst metal or metal oxide wherein saidmetal is selected from the group consisting of Groups IB, IIB, VIII andIIIA of the Periodic Table. Preferably, the metal is gallium, niobium,indium or zinc in the range of from about 0.05 to 5% by weight.

Xylene Isomerization

SSZ-58 may also be useful in a process for isomerizing one or morexylene isomers in a C₈ aromatic feed to obtain ortho-, meta-, andpara-xylene in a ratio approaching the equilibrium value. In particular,xylene isomerization is used in conjunction with a separate process tomanufacture para-xylene. For example, a portion of the para-xylene in amixed C₈ aromatics stream may be recovered by crystallization andcentrifugation. The mother liquor from the crystallizer is then reactedunder xylene isomerization conditions to restore ortho-, meta- andpara-xylenes to a near equilibrium ratio. At the same time, part of theethylbenzene in the mother liquor is converted to xylenes or to productswhich are easily separated by filtration. The isomerate is blended withfresh feed and the combined stream is distilled to remove heavy andlight by-products. The resultant C₈ aromatics stream is then sent to thecrystallizer to repeat the cycle.

Optionally, isomerization in the vapor phase is conducted in thepresence of 3.0 to 30.0 moles of hydrogen per mole of alkylbenzene(e.g., ethylbenzene). If hydrogen is used, the catalyst should compriseabout 0.1 to 2.0 wt. % of a hydrogenation/dehydrogenation componentselected from Group VIII (of the Periodic Table) metal component,especially platinum or nickel. By Group VIII metal component is meantthe metals and their compounds such as oxides and sulfides.

Optionally, the isomerization feed may contain 10 to 90 wt. % of adiluent such as toluene, trimethylbenzene, naphthenes or paraffins.

Oligomerization

It is expected that SSZ-58 can also be used to oligomerize straight andbranched chain olefins having from about 2 to 21 and preferably 2-5carbon atoms. The oligomers which are the products of the process aremedium to heavy olefins which are useful for both fuels, i.e., gasolineor a gasoline blending stock and chemicals.

The oligomerization process comprises contacting the olefin feedstock inthe gaseous or liquid phase with a catalyst comprising SSZ-58.

The zeolite can have the original cations associated therewith replacedby a wide variety of other cations according to techniques well known inthe art. Typical cations would include hydrogen, ammonium and metalcations including mixtures of the same. Of the replacing metalliccations, particular preference is given to cations of metals such asrare earth metals, manganese, calcium, as well as metals of Group II ofthe Periodic Table, e.g., zinc, and Group VIII of the Periodic Table,e.g., nickel. One of the prime requisites is that the zeolite have afairly low aromatization activity, i.e., in which the amount ofaromatics produced is not more than about 20% by weight. This isaccomplished by using a zeolite with controlled acid activity [alphavalue] of from about 0.1 to about 120, preferably from about 0.1 toabout 100, as measured by its ability to crack n-hexane.

Alpha values are defined by a standard test known in the art, e.g., asshown in U.S. Pat. No. 3,960,978 issued on Jun. 1, 1976 to Givens et al.which is incorporated totally herein by reference. If required, suchzeolites may be obtained by steaming, by use in a conversion process orby any other method which may occur to one skilled in this art.

Condensation of Alcohols

SSZ-58 can be used to condense lower aliphatic alcohols having 1 to 10carbon atoms to a gasoline boiling point hydrocarbon product comprisingmixed aliphatic and aromatic hydrocarbon. The process disclosed in U.S.Pat. No. 3,894,107, issued Jul. 8, 1975 to Butter et al., describes theprocess conditions used in this process, which patent is incorporatedtotally herein by reference.

The catalyst may be in the hydrogen form or may be base exchanged orimpregnated to contain ammonium or a metal cation complement, preferablyin the range of from about 0.05 to 5% by weight. The metal cations thatmay be present include any of the metals of the Groups I through VIII ofthe Periodic Table. However, in the case of Group IA metals, the cationcontent should in no case be so large as to effectively inactivate thecatalyst, nor should the exchange be such as to eliminate all acidity.There may be other processes involving treatment of oxygenatedsubstrates where a basic catalyst is desired.

Methane Upgrading

Higher molecular weight hydrocarbons can be formed from lower molecularweight hydrocarbons by contacting the lower molecular weight hydrocarbonwith a catalyst comprising SSZ-58 and a metal or metal compound capableof converting the lower molecular weight hydrocarbon to a highermolecular weight hydrocarbon. Examples of such reactions include theconversion of methane to C₂₊ hydrocarbons such as ethylene or benzene orboth. Examples of useful metals and metal compounds include lanthanideand or actinide metals or metal compounds.

These reactions, the metals or metal compounds employed and theconditions under which they can be run are disclosed in U.S. Pat. No.4,734,537, issued Mar. 29, 1988 to Devries et al.; U.S. Pat. No.4,939,311, issued Jul. 3, 1990 to Washecheck et al.; U.S. Pat. No.4,962,261, issued Oct. 9, 1990 to Abrevaya et al.; U.S. Pat. No.5,095,161, issued Mar. 10, 1992 to Abrevaya et al.; U.S. Pat. No.5,105,044, issued Apr. 14, 1992 to Han et al.; U.S. Pat. No. 5,105,046,issued Apr. 14, 1992 to Washecheck; U.S. Pat. No. 5,238,898, issued Aug.24, 1993 to Han et al.; U.S. Pat. No. 5,321,185, issued Jun. 14, 1994 tovan der Vaart; and U.S. Pat. No. 5,336,825, issued Aug. 9, 1994 toChoudhary et al., each of which is incorporated herein by reference inits entirety.

EXAMPLES

The following examples demonstrate but do not limit the presentinvention. The templating agent indicated Table C below is used in theseexamples.

TABLE C

The anion (X⁻) associated with the cation may be any anion which is notdetrimental to the formation of the zeolite. Representative anionsinclude halogen, e.g., fluoride, chloride, bromide and iodide,hydroxide, acetate, sulfate, tetrafluoroborate, carboxylate, and thelike. Hydroxide is the most preferred anion.

Example 1 Synthesis of N-butyl-N-cyclooctylpyrrolidinium hydroxide(Template A)

I. Synthesis of N-cyclooctylpyrrolidine

A three-neck 3000 ml. flask was charged with 75 gm. (1.05 moles) ofpyrrolidine, 51 gm. cyclooctanone (0.4 mole) and 80 ml. anhydroushexane. To the resulting solution, 80 gm. (0.8 mole) of anhydrousmagnesium sulfate was added and the mixture was mechanically stirred andheated at reflux (the reaction was monitored by NMR analysis) for 108hours. The reaction mixture was filtered through a fritted glass funnel.The filtrate was concentrated at reduced pressure on a rotary evaporatorto give 70.5 gm. of a clear (yellow-tinted) oily substance. ¹H-NMR and¹³C-NMR spectra were acceptable for the desired product,1-(1-pyrrolino)cyclooctene. Saturation of the 1-(1-pyrrolino)cycloocteneto give N-cyclooctylpyrrolidine was accomplished in 98% yield bycatalytic hydrogenation in ethanol at a 55 psi pressure of hydrogen gasin the presence of 10% Pd on activated carbon.

II. Quaternization (synthesis of N-butyl-N-cyclooctylpyrrolidiniumiodide)

To a solution of 60 gms. (0.33 mole) of N-cyclooctyl pyrrolidine in 600ml. anhydrous methanol, 150 gm. (0.825 mole) of butyl iodide was added.The reaction mixture was refluxed while stirring for four days. Then anadditional equivalent of butyl iodide and one equivalent (33 gm., 0.33mole) of potassium bicarbonate were added and the mixture was stirred atrefluxing temperature for an additional 36 hours. The reaction mixturewas concentrated at reduced pressure on a rotary evaporator to give anoff-white colored solid material. The solids were rinsed several timeswith chloroform and filtered after each rinse. All the chloroform rinseswere combined and concentrated to give a white powder whose NMR datawere acceptable for the desired quaternary ammonium iodide salt. Thereaction afforded 109 gm. (90% yield) ofN-butyl-N-cyclooctylpyrrolidinium iodide. The iodide salt was purifiedby recrystallization by completely dissolving the iodide salt inacetone, and then precipitating by the addition of ethyl ether to theacetone solution. This procedure gave 98 gms. of white powder with veryclean ¹H and ¹³C-NRM spectra.

III. Ion Exchange (synthesis of N-butyl-N-cyclooctylpyrrolidiniumhydroxide)

N-butyl-N-cyclooctylpyrrolidinium iodide salt (95 gms., 0.26 mole) wasdissolved in 300 ml. water in a 1000 ml. plastic bottle. To thesolution, 300 gms. of Ion Exchange Resin OH (BIO RAD® AG1-X8) was addedand the mixture was stirred at room temperature overnight. The mixturewas filtered and the solids were rinsed with an additional 250 ml. ofwater. The original mixture was filtered and the rinse were combined anda small amount was titrated with 0.1N HCl to indicate the presence of0.24 mol hydroxide (0.24 mol N-butyl-N-cyclooctylpyrrolidiniumhydroxide) in the solution.

The synthetic procedure described above is depicted below.

In a manner similar to that of Example 1,N-propyl-cyclooctylpyrrolidinium cation (Template B) can be prepared.

Example 2 Preparation of Borosilicate SSZ-58

A 23 cc. Teflon liner was charged with 6.9 gms. of 0.435M aqueoussolution of N-butyl-N-cyclooctylpyrrolidinium hydroxide (3 mmol,Template A), 1.2 gms. of 1M aqueous solution of NaOH (1.2 mmol NaOH) and3.9 gms. of deionized water. To the resulting mixture, 0.06 gm. ofsodium borate decahydrate (0.157 mmol of sodium borate decahydrate,about 0.315 mmol B₂O₃) was added and stirred until completely dissolved.Then 0.9 gm. of Cabosil-M-5 fumed SiO₂ (about 14.7 mmol SiO₂) was addedto the solution and the mixture was thoroughly stirred. The resultinggel was capped off and placed in a Parr bomb steel reactor and heated inan oven at 160° C. while rotating at 43 rpm. The reaction was monitoredby checking the gel's pH, and by looking for crystal formation usingScanning Electron Microscopy (SEM) at six day intervals. The reactionwas completed after heating for 12 days at the conditions describedabove. Once the crystallization was complete, the starting reaction gelturned to a mixture comprising a clear liquid layer with solids (powder)that settled to the bottom. The mixture was filtered through a frittedglass funnel. The collected solids were thoroughly washed with water andthen rinsed with acetone (10 ml.) to remove any organic residues. Thesolids were allowed to air-dry overnight and then they were oven-driedat 120° C. for one hour. The reaction afforded 0.78 gm. of a very finepowder. SEM showed the presence of only one crystalline phase. The X-rayanalysis of the powder indicated that the material was SSZ-58.

Examples 3-16 Synthesis of Borosilicate SSZ-58

The synthesis of Example 1 was repeated keeping the amount of NaOH,water and Cab-O-Sil M5 the same while varying the amount ofNa₂B₄O₇10H₂O. The SiO₂/OH mole ratio was 3.5, the H₂O/SiO₂mole ratio was45 and the SiO₂/B₂O₃ and SiO₂/Na mole ratios were as indicated in thetable below. The reactions were carried out at 160° C. and 43 rpm.

Example No. SiO₂/B₂O₃ SiO₂/Na Days Products 3 280 11.74 12 SSZ-58 4 14011.26 12 SSZ-58 5 93.6 10.83 12 SSZ-58 6 70 10.42 12 SSZ-58 7 56 10.0512 SSZ-58 8 46.3 9.7 12 SSZ-58 9 40 9.38 12 SSZ-58 10 35 9.07 12 SSZ-5811 31 8.8 18 SSZ-58 12 28 8.52 18 SSZ-58 + layered mat'l 13 25.5 8.27 18SSZ-58 + layered mat'l 14 23.3 8.03 18 SSZ-58 (major) + layered mat'l(minor 15 21.55 7.81 18 SSZ-58 (major) + layered mat'l (minor) 16 18.677.4 21 SSZ-58 + layered mat'l (minor)

Example 17 Synthesis of Aluminosilicate SSZ-58

A 23 cc. Teflon liner was charged with 5.2 gms. of 0.435M aqueoussolution of N-butyl-N-cyclooctylpyrrolidinium hydroxide (2.25 mmolTemplate A), 1.5 gms. of 1M NaOH aqueous solution (1.5 mmol NaOH) and0.75 gm. of deionized water. To the resulting solution, 0.25 gm. ofsodium-Y zeolite (Union Carbide LZ-Y52: SiO₂/Al₂O₃=5) and 0.80 gm. ofCabosil M-5 filmed SiO₂ (about 13 mmol SiO₂) was added, consecutively.The resulting mixture was thoroughly stirred and the resulting gel wascapped off and placed in a Parr bomb steel reactor and heated in an ovenat 160° C. while rotating at 43 rpm. The reaction was monitored bychecking the gel's pH, and by looking for crystal formation using SEM atsix day intervals. The reaction was completed after heating at theconditions described above for six days. The completed reaction mixtureappeared as a colorless liquid with fine white solid settled to thebottom of the Teflon liner. The mixture was filtered through a frittedglass funnel, and the obtained white solids were washed generously withwater and then rinsed with a small amount of acetone and allowed toair-dry overnight. The solids were further dried in an oven at 120° C.for one hour. The reaction yielded 0.81 gm. of SSZ-58.

Examples 18-32 Synthesis of Aluminosilicate SSZ-58

The synthesis of Example 17 was repeated using LZ-Y52 as the aluminumsource and Cab-O-Sil M5 as the SiO₂ source. The SiO₂/OH mole ratio was8.7, the H₂O/SiO₂ mole ratio was 28 and the SiO₂/Al₂O₃ and SiO₂/Na moleratios were as indicated in the table below. The reactions were carriedout at 160° C. and 43 rpm.

Example No. SiO₂/Al₂O₃ SiO₂/Na Products 18 317 8.4 SSZ-58 + Trace LZ-Y5219 158.5 8.1 SSZ-58 + Trace LZ-Y52 20 107.5 7.78 SSZ-58 + Trace LZ-Y5221 82.5 7.5 SSZ-58 22 66.9 7.3 SSZ-58 23 56.5 7.1 SSZ-58 24 49 6.9SSZ-58 25 43.5 6.7 SSZ-58 26 39 6.6 SSZ-58 + trace LZ-Y52 27 35.8 6.4SSZ-58 + trace LZ-Y52 28 33 6.26 SSZ-58 (mostly) + LZ-Y52 29 30.8 6.16SSZ-58 (mostly) + LZ-Y52 30 26.3 5.85 SSZ-58 (major) LZ-Y52 (minor) 3123.8 5.66 SSZ-58 (major) LZ-Y52 (minor) 32 20 5.32 SSZ-58 (major) LZ-Y52(minor)

Example 33 Synthesis of All-Silica SSZ-58

A 23 cc. Teflon liner was charged with 6.9 gms. of 0.435M aqueoussolution of N-butyl-N-cyclpyrrolidinium hydroxide (3 mmol Template A),1.2 gms. of 1M NaOH aqueous solution (1.2 mmol NaOH) and 3.9 gm. ofdeionized water. To the resulting solution, 0.9 gm. of Cabosil M-5 fumedSiO₂ (about 14.7 mmol SiO₂) was added and the mixture was thoroughlystirred. The resulting mixture was thoroughly stirred and the resultinggel was capped off and placed in a Parr bomb steel reactor and heated inan oven at 160° C. while rotating at 43 rpm. The reaction was monitoredby checking the gel's pH, and by looking for crystal formation using SEMat six day intervals. The reaction was completed after heating at theconditions described above for 18 days. The completed reaction mixtureappeared as a colorless liquid with solids (powder) settled to thebottom of the Teflon liner. The mixture was filtered through a frittedglass funnel. The collected solids were thoroughly washed with water andthen rinsed with acetone (10 ml.) to remove any organic residues. Thesolids were allowed to air-dry overnight and then dried in an oven at120° C. for one hour. The reaction yielded 0.73 gm. of pure SSZ-58

Example 34 Seeded Synthesis of Borosilicate SSZ-58

A 23 cc Teflon liner is charged with 6.9 gm of 0.435M aqueous solutionof N-butyl-N-cyclooctylpyrrolidinium hydroxide (3 mmol template), 1.2 gmof 1M aqueous solution of NaOH (1.2 mmol NaOH) and 3.9 gm of de-ionizedwater. To this mixture, 0.06 gm of sodium borate decahydrate (0.157 mmolof Na₂B₄O₇.10H₂O; ˜0.315 mmol B₂O₃) is added and stirred untilcompletely dissolved. Then, 0.9 gm of CABOSIL-M-5 (˜14.7 mmol SiO₂) and0.04 gm of SSZ-58 (the product of Example 1) is added to the solutionand the mixture is thoroughly stirred. The resulting gel is capped offand placed in a Parr bomb steel reactor and heated in an oven at 160° C.while rotating at 43 rpm. The reaction is monitored by checking thegel's pH, and by looking for crystal formation using Scanning ElectronMicroscopy (SEM). The reaction is completed after heating for 5 days atthe conditions described above. Once the crystallization is complete,the starting reaction gel turns to a mixture comprising of a clearliquid layer with solids (powder) that settled to the bottom. Themixture is filtered through a fitted-glass funnel. The collected solidsare thoroughly washed with water and, then, rinsed with acetone (10 ml)to remove any organic residues. The solids are allowed to air-dry overnight and, then, dried in an oven at 120° C. for one hour. The reactionaffords 0.85 gram of a very fine powder. SEM shows the presence of onlyone crystalline phase. The X-ray pattern of the powder is identical tothe XRD pattern of the product of Example 1.

Example 35 Calcination of SSZ-58

The material from Example 2 is calcined in the following manner. A thinbed of material is heated in a muffle furnace from room temperature to120° C. at a rate of 1° C. per minute and held at 120° C. for threehours. The temperature is then ramped up to 540° C. at the same rate andheld at this temperature for 5 hours, after which it is increased to594° C. and held there for another 5 hours. A 50/50 mixture of air andnitrogen is passed over the zeolite at a rate of 20 standard cubic feetper minute during heating. The product had the X-ray diffraction dataTable IIA above.

Example 36 NH₄ Exchange

Ion exchange of calcined SSZ-58 material (prepared in Example 35) isperformed using NH₄NO₃ to convert the zeolite from its Na⁺ form to theNH₄ ⁺ form, and, ultimately, the H⁺ form. Typically, the same mass ofNH₄NO₃ as zeolite is slurried in water at a ratio of 25-50:1 water tozeolite. The exchange solution is heated at 95° C. for 2 hours and thenfiltered. This procedure can be repeated up to three times. Followingthe final exchange, the zeolite is washed several times with water anddried. This NH₄ ⁺ form of SSZ-58 can then be converted to the H⁺ form bycalcination (as described in Example 35) to 540° C.

Example 37 Constraint Index Determination

The hydrogen form of the zeolite of Example 17 (after treatmentaccording to Examples 34 and 35) is pelletized at 2-3 KPSI, crushed andmeshed to 20-40, and then>0.50 gram is calcined at about 540° C. in airfor four hours and cooled in a desiccator. 0.50 Gram is packed into a ⅜inch stainless steel tube with alundum on both sides of the zeolite bed.A Lindburg furnace is used to heat the reactor tube. Helium isintroduced into the reactor tube at 10 cc/min. and at atmosphericpressure. The reactor is heated to about 315° C., and a 50/50 (w/w) feedof n-hexane and 3-methylpentane is introduced into the reactor at a rateof 8 μl/min. Feed delivery is made via an ISCO pump. Direct samplinginto a gas chromatograph begins after 10 minutes of feed introduction.The Constraint Index value is calculated from the gas chromatographicdata using methods known in the art, and is found to be 0.57. At 315° C.and 10 minutes on-stream, feed conversion was 37%.

It can be seen that SSZ-58 has very high cracking activity, indicativeof strongly acidic sites. The low value of the Constraint Index and thefouling rate of SSZ-58 are typical of a large pore zeolite. In addition,the low fouling rate indicates that this catalyst has a good stability.

Example 38 n-Hexadecane Cracking

The product of Example 17 is treated as in Examples 34 and 35. Then asample is slurried in water and the pH of the slurry adjusted to a pH of˜10 with dilute ammonium hydroxide. To the slurry is added a solution ofPd(NH₃)₄(NO₃)₂ at a concentration which would provide 0.5 wt. % Pd withrespect to the dry weight of the zeolite sample. This slurry is left tostand at room temperature for 72 hours. Then, the slurry is filteredthrough a fritted glass funnel, washed with de-ionized water, and driedat 120° C. for two hours. The catalyst is then calcined slowly up to482° C. in air and held there for three hours.

The calcined catalyst is pelletized in a Carver Press and crushed toyield particles with a 20/40 mesh size range. 0.5 gm of the catalyst ispacked into a ¼″ OD tubing reactor in a micro unit for n-hexadecanehydroconversion. Table III gives the run conditions and the productsdata for the hydrocracking test on n-hexadecane. After the catalyst istested with n-hexadecane, it is titrated using a solution of butyl aminein hexane. The temperature is increased and the conversion and productdata evaluated again under titrated conditions. The results shown inTable III show that SSZ-58 is an effective hydrocracking catalyst.

TABLE III Temperature 534° F. 582° F. Time-on-Stream (hrs.) 33.8-45.757.7-70.2 WHSV 1.55 1.55 PSIG 1200 1200 Titrated? No Yes n-16, %Conversion 97.7 99.4 Hydrocracking Conversion, % 70.1 79.6 IsomerizationSelectivity, % 29.4 24.4 Crack. Selectivity, % 70.6 78.1 C₄ ⁻, % 8.4 8.6C₅/C₄ 7.4 7.9 C₅ + C₆/C₅, % 25.8 28.3 DMB/MP 0.04 0.04 C₄-C₁₃ I/N 1.642.1

Example 39 Nitrogen Adsorption

The product of Example 2 is treated as in Examples 34 and 35. Then it issubjected to a surface area and micropore volume analysis using N₂ asadsorbate and via the BET method. The BET area is 326 m²/gm. Theexternal surface area of the zeolite is 88 m²/gm and the microporevolume is 0.11 cc/gm.

Example 40

Using a procedure similar to that of Example 2, SSZ-58 is prepared usinga N-propyl-cyclooctylpyrrolidinium cation (Template B) as the templatingagent.

What is claimed is:
 1. A process for converting hydrocarbons comprisingcontacting a hydrocarbonaceous feed at hydrocarbon converting conditionswith a catalyst comprising a zeolite having a mole ratio greater thanabout 20 of an oxide of a first tetravalent element to an oxide of asecond tetravalent element which is different from said firsttetravalent element, trivalent element, pentavalent element or mixturethereof and having, after calcination, the X-ray diffraction lines ofTable II.
 2. The process of claim 1 wherein the zeolite is predominantlyin the hydrogen form.
 3. The process of claim 1 wherein the zeolite issubstantially free of acidity.
 4. The process of claim 1 wherein theprocess is a hydrocracking process comprising contacting the catalystwith a hydrocarbon feedstock under hydrocracking conditions.
 5. Theprocess of claim 4 wherein the zeolite is predominantly in the hydrogenform.
 6. The process of claim 1 wherein the process is a dewaxingprocess comprising contacting the catalyst with a hydrocarbon feedstockunder dewaxing conditions.
 7. The process of claim 6 wherein the zeoliteis predominantly in the hydrogen form.
 8. The process of claim 1 whereinthe process is a process for improving the viscosity index of a dewaxedproduct of waxy hydrocarbon feeds comprising contacting the catalystwith a waxy hydrocarbon feed under isomerization dewaxing conditions. 9.The process of claim 8 wherein the zeolite is predominantly in thehydrogen form.
 10. The process of claim 1 wherein the process is aprocess for producing a C₂₀₊ lube oil from a C₂₀₊ olefin feed comprisingisomerizing said olefin feed under isomerization conditions over thecatalyst.
 11. The process of claim 10 wherein the zeolite ispredominantly in the hydrogen form.
 12. The process of claim 10 whereinthe catalyst further comprises at least one Group VIII metal.
 13. Theprocess of claim 1 wherein the process is a process for catalyticallydewaxing a hydrocarbon oil feedstock boiling above about 350° F. andcontaining straight chain and slightly branched chain hydrocarbonscomprising contacting said hydrocarbon oil feedstock in the presence ofadded hydrogen gas at a hydrogen pressure of about 15-3000 psi underdewaxing conditions with the catalyst.
 14. The process of claim 13wherein the zeolite is predominantly in the hydrogen form.
 15. Theprocess of claim 13 wherein the catalyst further comprises at least oneGroup VIII metal.
 16. The process of claim 13 wherein said catalystcomprises a layered catalyst comprising a first layer comprising thezeolite and at least one Group VIII metal, and a second layer comprisingan aluminosilicate zeolite which is more shape selective than thezeolite of said first layer.
 17. The process of claim 1 wherein theprocess is a process for preparing a lubricating oil which comprises:hydrocracking in a hydrocracking zone a hydrocarbonaceous feedstock toobtain an effluent comprising a hydrocracked oil; and catalyticallydewaxing said effluent comprising hydrocracked oil at a temperature ofat least about 400° F. and at a pressure of from about 15 psig to about3000 psig in the presence of added hydrogen gas with the catalyst. 18.The process of claim 17 wherein the zeolite is predominantly in thehydrogen form.
 19. The process of claim 17 wherein the catalyst furthercomprises at least one Group VIII metal.
 20. The process of claim 1wherein the process is a process for isomerization dewaxing a raffinatecomprising contacting said raffinate in the presence of added hydrogenunder isomerization dewaxing conditions with the catalyst.
 21. Theprocess of claim 20 wherein the zeolite is predominantly in the hydrogenform.
 22. The process of claim 20 wherein the catalyst further comprisesat least one Group VIII metal.
 23. The process of claim 20 wherein theraffinate is bright stock.
 24. The process of claim 1 wherein theprocess is a process for increasing the octane of a hydrocarbonfeedstock to produce a product having an increased aromatics contentcomprising contacting a hydrocarbonaceous feedstock which comprisesnormal and slightly branched hydrocarbons having a boiling range aboveabout 40° C. and less than about 200° C. under aromatic conversionconditions with the catalyst.
 25. The process of claim 24 wherein thezeolite is substantially free of acid.
 26. The process of claim 24wherein the zeolite contains a Group VIII metal component.
 27. Theprocess of claim 1 wherein the process is a catalytic cracking processcomprising contacting a hydrocarbon feedstock in a reaction zone undercatalytic cracking conditions in the absence of added hydrogen with thecatalyst.
 28. The process of claim 27 wherein the zeolite ispredominantly in the hydrogen form.
 29. The process of claim 27 whereinthe catalyst additionally comprises a large pore crystalline crackingcomponent.
 30. The process of claim 1 wherein the process is anisomerization process for isomerizing C₄ to C₇ hydrocarbons, comprisingcontacting a feed having normal and slightly branched C₄ to C₇hydrocarbons under isomerizing conditions with the catalyst.
 31. Theprocess of claim 30 wherein the zeolite is predominantly in the hydrogenform.
 32. The process of claim 30 wherein the zeolite has beenimpregnated with at least one Group VIII metal.
 33. The process of claim30 wherein the catalyst has been calcined in a steam/air mixture at anelevated temperature after impregnation of the Group VIII metal.
 34. Theprocess of claim 32 wherein the Group VIII metal is platinum.
 35. Theprocess of claim 1 wherein the process is a process for alkylating anaromatic hydrocarbon which comprises contacting under alkylationconditions at least a molar excess of an aromatic hydrocarbon with a C₂to C₂₀ olefin under at least partial liquid phase conditions and in thepresence of the catalyst.
 36. The process of claim 35 wherein thezeolite is predominantly in the hydrogen form.
 37. The process of claim35 wherein the olefin is a C₂ to C₄ olefin.
 38. The process of claim 37wherein the aromatic hydrocarbon and olefin are present in a molar ratioof about 4:1 to about 20:1, respectively.
 39. The process of claim 37wherein the aromatic hydrocarbon is selected from the group consistingof benzene, toluene, ethylbenzene, xylene, naphthalene,dimethylnaphthalene, naphthalene derivatives or mixtures thereof. 40.The process of claim 1 wherein the process is a process fortransalkylating an aromatic hydrocarbon which comprises contacting undertransalkylating conditions an aromatic hydrocarbon with a polyalkylaromatic hydrocarbon under at least partial liquid phase conditions andin the presence of the catalyst.
 41. The process of claim 40 wherein thezeolite is predominantly in the hydrogen form.
 42. The process of claim40 wherein the aromatic hydrocarbon and the polyalkyl aromatichydrocarbon are present in a molar ratio of from about 1:1 to about25:1, respectively.
 43. The process of claim 40 wherein the aromatichydrocarbon is selected from the group consisting of benzene, toluene,ethylbenzene, xylene, or mixtures thereof.
 44. The process of claim 40wherein the polyalkyl aromatic hydrocarbon is a dialkylbenzene.
 45. Theprocess of claim 1 wherein the process is a process to convert paraffinsto aromatics which comprises contacting paraffins under conditions whichcause paraffins to convert to aromatics with a catalyst comprising thezeolite and gallium, zinc, or a compound of gallium or zinc.
 46. Theprocess of claim 1 wherein the process is a process for isomerizingolefins comprising contacting said olefin under conditions which causeisomerization of the olefin with the catalyst.
 47. The process of claim1 wherein the process is a process for isomerizing an isomerization feedcomprising an aromatic C₈ stream of xylene isomers or mixtures of xyleneisomers and ethylbenzene, wherein a more nearly equilibrium ratio ofortho-, meta and para-xylenes is obtained, said process comprisingcontacting said feed under isomerization conditions with the catalyst.48. The process of claim 1 wherein the process is a process foroligomerizing olefins comprising contacting an olefin feed underoligomerization conditions with the catalyst.
 49. A process forconverting lower alcohols and other oxygenated hydrocarbons comprisingcontacting said lower alcohol or other oxygenated hydrocarbon underconditions to produce liquid products with a catalyst comprising azeolite having a mole ratio greater than about 20 of an oxide of a firsttetravalent element to an oxide of a second tetravalent element which isdifferent from said first tetravalent element, trivalent element,pentavalent element or mixture thereof and having, after calcination,the X-ray diffraction lines of Table II.
 50. The process of claim 1wherein the process is a process for the production of higher molecularweight hydrocarbons from lower molecular weight hydrocarbons comprisingthe steps of: (a) introducing into a reaction zone a lower molecularweight hydrocarbon-containing gas and contacting said gas in said zoneunder C₂₊ hydrocarbon synthesis conditions with the catalyst and a metalor metal compound capable of converting the lower molecular weighthydrocarbon to a higher molecular weight hydrocarbon; and (b)withdrawing from said reaction zone a higher molecular weighthydrocarbon-containing stream.
 51. The process of claim 50 wherein themetal or metal compound comprises a lanthanide or actinide metal ormetal compound.
 52. The process of claim 50 wherein the lower molecularweight hydrocarbon is methane.